Adhesive compositions of NCO-terminated prepolymer and rubber

ABSTRACT

An adhesive composition having a long pot life and strong adhesive properties comprising (A) omega , omega &#39;&#39;diisocyanatodimethylcyclohexane, its polymer or NCO-terminated prepolymer and (B) natural rubber, synthetic rubber or a high molecular weight polyol.

United States Patent 1191 Matsui et al.

1451 Sept. 30, 1975 l l ADHESIVE COMPOSITIONS OF NCO-TERMINATED PREPOLYMER AND RUBBER [75] lnventors: Yutaka Matsui, Shizuoka; Seiji Kazama, Hyogo; Masamitsu Nakabayash'i; Koji Kobayashi, both of Osaka, all of Japan [73] Assigncc: Takeda Chemical Industries, Ltd.,

Osaka, Japan [22] Filed: June 28, 1972 [21] Appl. No.: 267,151

[30] Foreign Application Priority Data .Iul3- 5. 1971 Japan 46-49474 [52] US. Cl. .L 260/3; 161/190; 161/213;

161/214; 161/217; 161/242; 161/253; 161/254; 161/255; 260/2 A; 260/2 BP; 260/75 NK: 260/75 NT; 260/775 AM;

260/77.5 AN; 260/709; 260/858; 260/859 R; 156/334; 156/338; 156/327 [51] Int. Cl. C08L 75/06; COSL 75/08; C08L 15/00 [58] Field of Search. 260/3, 859 R, 75 NT, 77.5 AT

Primary E.\'aminerWilbert J. Briggs, Sr. Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [57] ABSTRACT An adhesive composition having a long pot life and strong adhesive properties comprising (A) w,w-diisocyanatodimethylcyelohexane, its polymer or NCO- terminated prcpolymer and (B) natural rubber, synthetic rubber or a high molecular weight polyol.

17 Claims, No Drawings ADHESIVE COMPOSITIONS OF NCO-TERMINATED PREPOLYMER' AND RUBBER This invention relates to novel adhesive compositions which have a long pot life and strong adhesive force".

Hitherto, there have been-prepared various kinds of isocyanate-based adhesive compositions, each comprising an isocyanatecomp'onent arid a material soluble and fusible therewith such as a non-vulcanized rubber mixture or a hydroxy group-containing compound'The isocyanates which are generally used' inthe conventional adhesive compositions 'of'the above type" are classified into the following-two groups, one being a relative high molecular compound having many isocyanato groups 'e.g. reaction product of "1 mole oftrim'ethylolpropane and 3 moles of tolylen'ediisocyanate, and other being a polyisocyanate mo'nonier'havin'g three or more isocyanato groups in the molecule,ia typicalexample of which is tris-(p-isocyanatophenyl) metliane. I

However, adhesive compositions using the latter polyisocyanate monomers are superior to those using the former high molecular isocyanatesin' view of compatibility with other resins, adhesive force, durability and'heat-resistance. For this reasoni the latter polyisocyanatemonomers, especially tris-(pisocyanatophenyl) methane, tri's-(4-iso'cyanophenyl)- thiophosphate and modified diphenylmethariediisocyanate are often used as isoc yanate component of the adhesive compositions of this type. I

I But, an adhesive composition using thepolyisocyanate monomer as mentioned above, especially, tris-(pisocyanatophenyl)-methane, has only a very short pot life when the polyisocyanate is admixed with the main adhesive component such as resins (e.g. ureaformaldehyde resin) and rubbers, especially nonvulcanized rubbers, and thus" its. workability is very poor. For example, i a mixture of tris-(p- .isocyanatophenyl)-methane and polychloroprene rubber has a short pot life, and thereforeits workability is very limited. Further, adhesive compositions of this type have also such a defect that their adhesive layer is so remarkably colored after adhesion that causes poor appearance of the substrates,,Therefore, theadhesive composition of this type is limited in the use as an adhesive agent, for example, the composition is hardly useful for adhesionof light .-color materials such as light color shoes and bags, for which conventional adhesive compositions .using the polyisocyanatemonomer (e.g. tris-(p-isqcyanatophenyl) methane). are frequently used. ln order to overcome this defect, as. isocyanate component of the adhesive compositions, the use of tri-. s-(4-isocyanophenyl)-thiophosphate has been proposed, but an adhesive composition this compound also has a defect in. its remarkably short pot life, and thus it is substantially difficult to put .the adhesive composition into practical use. v I

Under these circumstances, the present inventors havemade extensive studies on isocyanate-based adhesives for the prupose of providing isocyanate-basedadhesives having a-sufficiently long pot life,- a strong adhesive force and not being susceptible to coloring, and unexpectedly found that an adhesive composition, using (0,00'-diisocyanato-dimethylcyclohexane (abbreviated as H 'XDI) as'an isocyanatecomponent can-exceptionally attain this purpose..- 1 Y The' present'invention hasbeen accomplished onthe above unexpected, finding.

pentane-dlol), alicyclic glycols having up:to 20 carbon therewith. I 1 v hydroxyethyl )ether, hydroxyethyl phenyl)ether]; polyols having 3 to 8 OH- Thus, the principal and essential object of the present invention-is to provide isocyanate-based adhesive compositions. having a sufficiently long pot life and a strong adhesive force and, not being susceptible to coloring. And, this object can be attained by using w,w'-dissocyanato-dimethylcyclohexane as an isocyanate component in'an adhesive compositionwhichcomprises an isocyanate component and a, material soluble and fusible The adhesive compositionof the present invention comprises the'following component (A) and the com- 'ponent (B), the component (A) being 'w,w'diisocyanato-dimethylcyclohexane, its polymer or its NCO- terminated prepolymer, and the component-(B) being .natural or-synthetic rubber or a highmolecular polyol. 10,0)'-Diisocyanato-dimethylcyclohexane employable in the present invention includes w,w'-diisocyana'to- 1 ,3-dimethylcyclohexane w,w" diisocyanato-1 ,4-dimethylcyclohexane and a mixture thereof. The polymer of w-,w-diisocyanato-dimethylcyclohexane includes all compounds having a urethodione ring or isocyanurate ring in their molecules and NCO-content of about 5 to about 35,- more-preferably about" 10 'to' about 25%,

-. which are prepared by polymerization of the isocyanate after a conventional manner such as polymerization of H XDI with the use of a basic-catalyst (e.g. trimethylbenzylammonium hydroxide). The above polymerization reaction is usually conducted at about 0 to about C in :a suitable inert solventJ-The reaction time varieswith a kind of catalyst to be used, but usually about3 to 20 hoursJThe solvent employable in the reaction includes esters (e.g.ethyl acetate,'butylacetate), ethers (e.g. diisopropyl ether) and ketones (e.g. methyl ethyl ketone).

Typicalexamples of the polymers are a dimer of H XDI and a trimer of H XDL'Namely, the predominant product of the polymerization reaction is a dimer =of H XDI, a trimer of H XDI or a mixture thereof, but

when the reaction conditions are rather mild, the product containsalsounreacted H XDI, and when the reactionconditions are rather severe, the product contains also higher polymerized polymers of H XDI. All of these mixtures however, can substantially equally be used in the present invention.

But, when the polymer contains unreacted H XDI, the unreacted diisocyanatemay be removed'by a suitable means (e.g. extraction, distillation), if necessary. The NCO-terminated prepolymer of H XDI is that prepared by reacting an excessamount of H XDI with a active hydrogen-containingcompound. The. active hydrogen-containing compound, which is used for the reaction with H XDI is preferably that having a molecular. weight of about 60-to about 500, particularly about 350 to' about 400', and is exemplified by saturated or unsaturated glycols such as aliphatic glycols having up to :12 carbonatom's (e. g.-ethylene glycol, diethylene glycol, 1,2-and 1,3-propylene glycol, 'l,2-,' 1,3-and 1,4-butylene glycol, '2,2-dimethyl-l,'3- propylene glycol, 1,6-hexane diol, 2,2,4-tri-methyl-l,3-

atoms [c.g. 2,2,4,4.-tetramethyl-cyclobutane diol, 1,3- cyclopentane, diol, I --l,4-cyclohexane.= diol,-' 1,4- bis(hydroxymethyl)cyclohexane, methylenebis('cycl'ohexanol)].and aromatic glycols having up to 20.; carbony atoms. .[e..g. l,4-phenylene-bis(B- isopropylidene-bis( B- groups per molecule, such as triol having up to 12 carbonatoms (e.g. trimethylolpropane, glycerol, hexane- -triol), tetraol having up to 14 carbon atoms (e.g.-pentaerythritol, diglycerol), sorbitol and sucrose;- primary amines which may be substituted=.=by'a lower alkoxy gr'oup- (e.g. methoxy, ethoxy, propoxy) such as aliphatic primary amines having -upto 20 carbon atoms (e.g. n-butylamine), alicyclic primary amines having up to 20 carbon atoms (e.g. cyclohexylamine), diamines such as aliphatic diamines having up to 20 carbon atoms (e.g. ethylenediamine, 1,6- hexamethylenediamine), alicyclic diamines having up to 20 carbon atoms (e.g. l,3-diaminomethylcyclohexane, isophoronediamine) and aromatic diamines having up to 20 carbon atoms (e.g. phenylenediamine, 4,4-diaminodiphenylmethane); mono-aminoalcohols having -up to 20 carbon atoms (e.g. ethanolamine, diethanolamine); carboxylic acids such as aliphatic mono-and diaminocarboxylic acid, alicyclic mono-- diaminocarboxylic acid, aliphatic hydroxy carboxylic acid, aromatic hydroxy carboxylic acids, mercapto acids, aliphatic dior .tricarboxylic acids having up to 20 carbonatoms (e.g. adipic acid, citric acid).

'The NCO-terminated ,prepolymer of the-present invention is prepared, as briefly stated above, by reacting um)-diisocyanato-dimethylcyclohexane or its polymer as mentioned above vwith the active hydrogencontaining compound or an optional mixture thereof in such an amount that a ratio of NCO groups/OH groups is not; lower than about 1.5, practically about 1.5 to about 10 more preferably about 1.8 toabout 3. When used in a too large amount of the diisocyanate, some of it remains unreacted.-;ln such a case, it is desirable to remove the unreacted diisocyanate by asuitable means (e.g. extraction-or distillation), but even when this purification procedure is not conducted, the remaining unreacted diisocyanate gives no bad influence upon the adhesive force when the resultant as such is used as one of the components .Of the adhesive composition.

The afore-mentioned reaction is usually conducted at about to about 150C in the absence or presence of an inert solvent.

.-ln. order. to :acceleratethe reaction, organic metal compounds (e.g. stannous octoate, ferric acetylacetonate; lead naphthenate) ortertiary amines (e.g. triethylenediamine, N-methylmorpholine) may be used in this reaction, and gellation inhibitors (e.g. benzoyl chloride) may also be used;

In the above-reaction, allophanate linkages or/and biuret linkages can be produced by conducting the reaction at a higher temperature than that mentioned above, or by using a catalyst such as stannous octoate.

The' inert solvent employable' in the reaction includes, for example, aromatic hydrocarbons (e.g. benzene, toluene xylene), halogenated hydrocarbons (e.g.

methylene chloride, ethylene chloride, trichloroethane, chlorobenzene), esters (e.g. ethyl acetate, butyl acetate, '2-ethoxyethyl acetate), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone), ethers (e.g. diisopropyl ether, tetrahydrofuran, dioxane), dimethyl formamide and dimethylacetamide. i

The natural rubber may be any ones which are produced in any place of origin and time.

T he syntheticrubber of the component (B) is a polymeror copolymer which is prepared by polymerization or copolymferization of a diene-type "compound having a conjugated double'bond and having '4 to carbon atoms in its molecule. The diene compound includes,

for example, butadiene, isoprene, chloroprene. The

per molecule, which includes, for example, styrene, ac-

rylonitrile, butylene, isobutylene. The molecular weight of the synthetic rubber is about 20,000 to about 200,000.

As the synthetic rubber of the component (B), any ones can equally be used regardless of their crystallinity, crystal structure, stereo structure, ect. The typical examples of the synthetic rubbers are styrenebutadiene rubber, butadiene rubber and nitrile rubber, chloroprene rubber, isoprene rubber and butyl rubber. Moreover, the synthetic rubber of the component (B) includes also other synthetic rubbers such as urethane rubbers, which are prepared by reacting isocyanate compound (e.g. diphenylmethane-4,4-diisocyanate) with polyester polyol or polyether polyol such as those mentioned hereinafter after per se converitional means.

The high molecular polyol of the component (B) is that having a molecular weight of about 400 to about 50,000, more preferably about 5,000 to about 30,000 and is exemplified by polyester polyols, polyether polyols, polyetherpolyester polyols and a mixture thereof. The polyester polyols include for example, polyester polyols which are prepared by reacting one or more of the glycols or the polyols having 3 to 8 OH groups per molecule as mentioned above with one or more of dicarboxylic acids as saturated aliphatic ones (e.g. adipic acid, sebacic acid), unsaturated aliphatic ones (e.g. maleic acid, fumaric acid) and aromatic ones (e.g. phthalic acid, isophthalic acid). The polyether polyols includes, for example, polyether polyols which are prepared by subjecting cyclic ethers such as ethylene oxide, propylene oxide, epichlorohydrin, oxacyclobutane, substituted oxacyclobutane, tetrahydrofuran to ringopening polymerization or compolymerization in the presence or absence of the glycol or the polyols having 3 to 8 OH groups per molecule as mentioned above. The polyether polyester polyols are prepared by reacting one or more of the glycols or the polyols having 3 to 8 OH groups per moleculeas mentioned above with cyclic ether is mentioned above and aromatic or unsaturated aliphtic dicarboxylic acid anhydride such as phthalic anhydride, and maleic anhydride.

Detailed reaction techniques or conditions for the production of the polyols may be any of conventional ones described in prior publications (e.g. High Polymers Vol. XVI Polyurethanes: Chemistry and Technology Part I (1962) by J. H. Saunders and K. C. Frisch, published by Interscience Publishers, New York, N.Y., U.S. Pat. Nos. 2890208, 2977885, 2933478, etc.).

Among the natural or synthetic rubbers and the high molecular polyols, the synthetic rubbers, especially chloroprene rubber is practically most preferable as the component (B). The synthetic rubbers of the component (B) may be incorporated with various additives such as antioxidants, reinforcing materials (e.g. magnesium oxide, zinc oxide, carbon black, stearic acid), solvents (e.g. toluene, methyl ethyl ketone, process oil) and materials adjusting viscosity (e.g. chlorinated rubber); etc.

The adhesive composition of the present invention is prepared by mixing the component (A) with the component (B) in such a ratio as mentioned hereinafter. In this mixing process, any inert organic solvent mentioned above may concomitantly be used in order to adjust the solid content and/or the NCO-content of the composition.

The adhesive composition of the present invention "'l comprises generally 1 weight part of the component- (A) and to 200 weight parts, more preferably to 100' weight parts of the component (B). The present adhesive compositions may be used as they are, but; if necessary, they may be used after dilution with such an n,

inert organic solvent as mentioned above. In thiscase,

the total solid content of the composition is generally adjusted to about 5 't o 70, m'Qre'preferaBly about 10 to about 50 weight %l in order further to 'enhanc'estabil'ity of the composition,-various additives such as "antioxidants, ultraviolet ray absorbers, hydrolysis'inhibitors and antifungal agents may befurther addedzto the compositionin an amount notexceeding about 5 weight of the solidcontent thereof. The thus prepared adhesive compositions of the present invention have a sufficiently long pot life and strong adhesive force. Further, if desired, the pot life may be optionally shortened by using a suitable catalyst (e.g.

N-methylmorpholine, stannous octoate, lead naphthenate) in an amount of about 0.1 to about 3.0%, and the pot life thus shortened ranges from a few seconds toseveral ten hours due to the catalyst amount., Further,

even after the adhesive composition of the present inanate of solid content of and an NCO-content of 352%. This product is referred to as component (A)- (i):

ii. A sirnilar r e i ibn' 'ves'se1to ,that used in'E'xperiment I.]-(.i) is charged with 53 parts of ethyl acetate and 5 8. 8iparts of to',w'- diisocyanato-1,3-dimethylcyclohexane. Then, to the solution is added dropwise over ljhour 14. 2 parts of w,w'-diaminomethylcyclohexane at 10 to 20C with stirring under dry nitrogen gas stream,--followed by-allowing to react at 70C for further 2 hours. After cooling the reaction system at 20C,

parts methylene chloride is added This proceiii. A similar reactio'n'vesse 1 iiiiiit' used if] Experimen,t [I]-(i) is charged with 15 partsof ethyl acetate, 85 parts of m,rp -diisocyanato--l ii dirnethylcyclohexane and 0.1 part of trimethylbenzylammonium hydroxide, followed by allowing to react at 45C for 10 hours. The resulting reaction mixture is extracted 6 times with a 1 mixture ofbenzene and-n-hexane (3:7),- and to the exvention is applied to substrates, there is not'observed coloring which has been the most serious'drawback in adhesive compositions using conventioned organic When the thus prepared present composition is used.-

as an adhesive agent, the technique for the adhesion may be any of conventional onesJFdr example, a substrate is immersed into the composition, orcomposition is appliedon the surface of a substrate, if necessary followed by removinga part or all of the solvent used; and drying, and thus .ltreatedsubstra-te is part on another substrate or thus treated substrates are piled on each other, followed by keeping. standing at room'temperature under atmospheric pressure or, i f necessary,

heating preferably und'er" elevated pressure;

The "following experiments are given to"illustrat e'this invention and should by no means be construed as limiting the scope'of this invention. The term-part(s)"" in the following experiments is based on weight.

EXPERIMENT 1) [-1]. Preparation of component (A) i. A reaction vessel equipped with a thermometer, a

'nitrogen gas inlet, areflux-cond'enser and a stirrer-,is

charged with 24. parts of ethyl acetate and 582 parts of w,w'-dii socyanatol ,3 dimethyicyclohexane. Then to the solution is added dropwise over, 1 ,hour 13.4 parts of trimethylolpropane at 50 to 70C with stirring under dry nitrogen 'gas stream, followed bywallowin'gto react I at 70C for further 2-hours;-After:c0oling.the;reaction system at 20C, 262 parts of methyleneixhloride is added. This procedure gives a. p oly u'r ethane. pol. isocy- 23 aromatic isocyanate, and a strong adhesive force at tract is added ethyl acetate in order to adjust a solid content thereof to 65 This procedure gives a reaction product of an NCO-content of 14% and viscosity of Gardner-D. To parts of the product is added 225 parts of methylene chloride, and the mixture is stirred to give an isocyanate polymer of solid content of 20% and-an NCO-content of 4.3%, which chiefly consists of HQQDI trimer. This product is referred to as component ('A)-(iii). iv. A similar-reaction vessel to that used in Experiment [I]-(i) is charged with 13.8 parts of ethyl acetate, 142.2 parts of methylene clif lorijde :and, 38.8 parts of co,w'-diisocyanato-l,3-dimethylcyclohexane. The solution is stirred at 20C for 1 hour under dry nitrogen gas stream, whereby a diisocyanate solution of solid content of 20% and an NCOcontent of 8.64%. Thisproduct is rfeferredto as a component (ZM-(iv) v. Ascoiit'rols, thefollo wing; components ('C) -(i to '(iii) are prepared by the'sarne manner asEx'periment l] -(i) except that the following diiso cyan ates are used in" place of w,w'-diis ocy'anato-l,3-dimethylcyclohexane:

,Component I Qiisocyanate tolylene dii'so'cyanate (2;4isomer/2,6-isomer=80l20 xylylene diisocyanate hexamethylene diisocyanate [IT] Preparation of adhesive compositions'""' l.'-.The adhesive compositions'zof the present invention are prepared by admixing the above components (A) with thefollowing component (B) in such a'ratio asdescribed in,the following Table (I). I

The component (B): (a mixture consisting of the following components):

Neoprene AD (trade name of l00 chloroprene rubber' manufactured by du-Pont de Nemours & Co. lnc. U.S.A. Magnesium oxide 4 Chlorinated rubber 25 Antioxidant 2 Zinc oxide 5 Methyl ethyl ketorie 325 Toluene I 77 Tablefl) Adhesive Constants of composition Component (part) Compositions (A)- (A)- (A)- (A)- (B) Solid Viscosity content (25C (i) (ii) (iii) (iv) (7r) cps. I

l-(i) 5 I 25 6,500 2-(i) I00 25 6,480 3-(i) 5 I00 25 6,250 4-(i) 5 100 25 6,300

2. As controls, the following adhesive compositions of Table (II) are prepared by the samemanner as in Experiment (Il) except that the above components (C)- (i) to (iii) and the following isocyanates are usedin place of the components (A)-(i) to (iv):

The isocyanates used are: tris-(pisocyanatophenyl)methane or tris-(4-isocyanophenyl)- thiophosphate.

As clear from theabove data, the pot life of the adhesive compositions of the present invention is remark ably longer than that of the controlled compositions and, moreover, can optionally be con-trolled i.e. shortenedby using a catalyst such as N-methylmorpholine.

On the contrary/the pot life of controlled compositions, especially the composition 4 and 5, are remarkably short. M

Table (II) 9 Component (part) Constants of Controlled composition composition (C)- (C)- (C)- TIM* TIT** (B) Solid Viscosity (i) (ii) (iii) content c.p.s

I 5 I00 25 6,500 2 5 I00 25 6,300 3 5 I00 25 6,300 4 5 109 25 6.200 5 5 I00 25 6,200

Remarks: 'Tris-( p-isocyunnto-phenyl )-meth1\nu "Tris-(4-isocyunophunyl)-thiophosphutc [III] Comparison of pot life To the adhesive compositions prepared in [II] are added various amounts of N-methylmorpholine in such [IV] Test of adhesive force. a ratio as described in the following Table (III) in order 40 to control the pot life.

The comparison of the adhesive compositions mentioned above in their pot lives is conducted by measuring a time required for making the compositions show no longer fluidity. Results are described in the following Table (III).

Table (Ill) Amount of catalyst l. Adhesivefo rce of the above adhesive compositions is tested by the following method:

The surface of a sole made of a mixture of natural rubber and butadiene-styrene rubber is roughed by sanding. One of the above adhesive composition is coated on the thus treated surface of the sole and the surface of a p olyvinyl 'chloride resin'sheet which is previously treated with a primer, followed keeping at room temperature for 30 minutes. Then, the thus treated sole and a polyvinyl chloride resinsheet are piled in such a manner that the coated surfaces are contacted with each other, followed by pressing. The piled material is pressed under pressureof 3.5kg/cm for 5 minutes, followed by keeping at room temperature for 1 week. The resultant is cut into'a test piece X 25 mm), and on thus prepared test piece, T-peeltest is conducted according to a .test method of ASTM D1876-69 by using'a Tensilon testing machine at a loading rate ofSOmm/i'nin. Results are described in the I following Table (IV).

In additionthe piled materials'prepared :in the above procedure a'r'e'stored'at'room temperature for 1 month in order to obseive'their coloring." Results are also described'inthe fbnowihgTable ('IV).

4 color Remark: type of destruction i Q G rubber suhstratcjs dqstructed v l C adhesive layer on the surface ofrubber substrate is peeled ofi' A adhesive layer on the surface of polyvinyl chloride substrate is peeled off.

() 2 no appreciable color change is observed.

As clear from the above data, the controlled compositions not being susceptible to colo'ri'ng shown "only a poor adhesive force. and 6h the c 'onitraryfjthe controlled compositionsshowing a relatively strong adhesive force are susceptible'tocolofingsBut, the adhesive compositions of the prese'ntiinvention show a strong adhesive force and, moreover, areriot susceptible to col:

Experiment Rubber mixture:

Neoprene AD I parts Magnesium oxide 4 parts Stearic acid 0.5 part Carbon black 58 parts Process oil 12 pars Zinc oxide parts Antioxidant 0.5 part The resultant shows very tight and strong adhesive force between the steel plate and the rubber component.

Experiment 3 Each surface of two steel plates to be adhered to each other is mechanically roughed in a similar manner to that of Experiment (2). A mixture of the component (A)-(ii) and (A)-(iii) [component (A)-(ii) compo nent (A)-(iii) 1:1 (weight)] is coated on the thus treated surfaces, and then the two plates are piled in s such samann'er that-:thetwo'rcoated surfaces are contacted with each other, followed by heating at 130C underpressureof l kg/cmifor 2 hours. The resultant shows satisfactory heat resistan'ce .and very tight-and strong adhesivexforce between the steel plates.

w L a I Experiment 4 To a l9 4 parts of q -diis ocyanato-1,3-dimethylcyclohexan e. kept at a temperature of 70C is addeddropwise over'30 rhinutes 1 6.6 parts of diglycerol under stirring, followedby allowing to react for further 3 hours at 75 to 80C. Then, tothe resulting reaction mixture is added 842 parts of ethyl acetate. This procedure gives a'polyurethane polyisocyanate of solid content of and an NCOcontent of 6.2%.

3 Parts of the thus prepared polyurethane polyisocyanate is admixed with 100 parts of thesame" component jec'tin g to thesame adhesive force test as inExperiment above composition a Experiment-5 The reaction productiwhicli is prepared reacting 77.6 parts of mgb diisocya'natoll 3 -dir'riethylcyclohexan e with 10 parts of N-methyldi ethariolamine is ex- 5 i. W v 4 tra ted with n-hexane to remove unreacted m,m-dnsoeast-eat as are;

Parts of the thus prepared polyurethane lp'ol yisogamers admixed with 'lOi) parts of thesarne 'coniponent as used in Experiment 1' n '1'. The. adhesive composition ipmtd shows ahigh peel" strength by the same test as Experiment l l Experiment- 6 I To 30 parts of polyester polyol having a molecular weight of about 20,000 which is prepared by reacting 0.5 mole of isophthalic acid and 0.5 mole of terephthalic acid with 0.52 mole of neopentylglycol and 0.5 1 mole of ethyleneglycol are added 35 parts of ethyl acetate and 35 parts of methyl ethyl ketone. To the resulting solution is added 10 parts of the component (A)- (i), and the resulting mixture is applied on the surface of aluminium foil in an amount 9.2 glm followed by keeping the foil standing at room temperature for 10 minutes to remove the solvent. The thus treated aluminium foil is piled on polyethyleneterephthalate film in such a manner that so-treated is contacted with the polyethyleneterephthalate film, followed by heating at C for 30 minutes.

The peel strength of g/l5mm(25C).

The peel strength of the resultant which prepared by the same manner as the above procedure except that the polyester polyol solution is only used in place of the mixture of the polyester polyol and the component (A)-(i) is merely 45 g/l5mm (25C).

the resultant is 690 Experiment 7 Influence of a ratio of component (A) /component (B) upon the adhesive force is examined below.

The following adhesive compositions l to 5 are prepared by admixing the component (A)-(ii) in Experiment (1)-[I] with the component (B) in Experiment (l)-[lI] in the ratios as listed in the following Table Adhesive forces of' these compositions .l -to 5 are .-tested in the same manner as in Experiment (l)-.[lV]

to give the results as described in the Table (V).

Table (V) I Component (part) Pcl strength Adhesive (kg/25 mm) composition (fU-(ii) (B) 25C 80C 3 I00 l0.50 5.4l 4 I00 12.50 7.00 5 13.20- 7.40

What we claim is: 1. An adhesive composition which comprises an .NCO-terminated prepolymer prepared by reacting w,m'-diisocyanato-dimethylcyclohexane with anactive hydrogen-containing compound having a molecular weight of about 60 to about 500 in a ratio of NCO groups to OH groups of not less than about 1.5 and a conjugated diene rubber, wherein the weight ratio of the NCO-terminated prepolymer to the rubber is about 0 wherein the active hydrogen-containing compound is a polyol having 3 to 8 QH groups per molecul e 5. An adhesive composition claimed in claim 1, wherein the rubber is natural rubber.

6. An adhesive composition claimed in claim 1,

wherein the rubber is a synthetic rubber.

7. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a polymer or copolymer which is prepared by polymerization or copolymerization of a diene-type compound having a conjugated double bond and having 4 to 10 carbon atoms in its molecule.

8. An adhesive composition claimed in claim 7, wherein the diene compound is a member selected from the group consisting of a butadiene, isoprene and chloroprene.

9. An adhesive composition claimed in claim 7, wherein the monomer copolymerizable with the diene compound is that having a double bond and 4 to 16 carbon atoms per molecule.

10. An adhesive composition claimed in claim 9, wherein the monomer copolymerizable with the diene compound is a member selected from the group consisting of styrene, acrylonitrile, butylene and isobutylene.

11. An adhesive'composition claimed in claim 10, wherein the molecular weight of synthetic rubber is about 20,000 to about 200,000.

12. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a styrene-butadiene rubber.

13. An adhesive composition claimed in claim 6,

wherein the synthetic rubber is a butadiene rubber.

14.,An adhesive composition claimed in claim 6, wherein the synthetic rubber is a nitrile rubber.

15. An adhesive composition claimed in claim 6,

wherein the synthetic rubber is a chloroprene rubber.

16. An adhesivecomposition claimed in claim 6, wherein the synthetic rubber is an isoprene rubber.

17. An adhesive composition claimed in claim 6,

wherein the synthetic rubber is a butyl rubber. 

1. AN ADHESIVE COMPOSITION WHICH COMPRISES AN NCO-TERMAINTED PREPOLYMER PREPARED BY REACTING W,W''-DIISOCYANATODIMETHYLCYCLOHEXANE WITH AN ACTIVE HYDROGEN-CONTAINING COMPOUND HAVING A MOLECULAR WEIGHT OF ABOUT 60 TO ABOUT 500 IN A RATIO OF NCO GROUPS TO OH GROUPS OF NOT LESS THAN ABOUT 1.5 AND A CONJUGATED DIENE RUBBER, WHEREIN THE WEIGHT RATIO OF THE NCO-TERMINATED PREPOLYMER TO THE RUBBER IS ABOUT 1/10 TO ABOUT 1/200.
 2. An adhesive composition claimed in claim 1, wherein the ratio of the NCO-terminated prepolymer to the rubber is about 1/15 to about 1/100.
 3. An adhesive composition claimed in claim 1, wherein the active hydrogen-containing compound is saturated or unsaturated glycol.
 4. An adhesive composition claimed in claim 1 wherein the active hydrogen-containing compound is a polyol having 3 to 8 OH groups per molecule.
 5. An adhesive composition claimed in claim 1, wherein the rubber is natural rubber.
 6. An adhesive composition claimed in claim 1, wherein the rubber is a synthetic rubber.
 7. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a polymer or copolymer which is prepared by polymerization or copolymerization of a diene-type compound having a conjugated double bond and having 4 to 10 carbon atoms in its molecule.
 8. An adhesive composition claimed in claim 7, wherein the diene compound is a member selected from the group consisting of a butadiene, isoprene and chloroprene.
 9. An adhesive composition claimed in claim 7, wherein the monomer copolymerizable with the diene compound is that having a double bond and 4 to 16 carbon atoms per molecule.
 10. An adhesive composition claimed in claim 9, wherein the monomer copolymerizable with the diene compound is a member selecTed from the group consisting of styrene, acrylonitrile, butylene and isobutylene.
 11. An adhesive composition claimed in claim 10, wherein the molecular weight of synthetic rubber is about 20,000 to about 200,000.
 12. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a styrene-butadiene rubber.
 13. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a butadiene rubber.
 14. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a nitrile rubber.
 15. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a chloroprene rubber.
 16. An adhesive composition claimed in claim 6, wherein the synthetic rubber is an isoprene rubber.
 17. An adhesive composition claimed in claim 6, wherein the synthetic rubber is a butyl rubber. 